An alkaline earth metal carboxylate phosphite stabilizing composition



United States Patent ()fiice 3,356,617 Patented Dec. 5, 1967 ABSTRACT 9F THE DISCLOSURE Asymmetric alkaline earth metal carboxylate phosphites, having attached to an atom of an alkaline earth metal both an organocarboxylic acid radical having 4 to '18 carbon atoms and a dihydrocarbon-phosphite radical that has 4 to 18 carbon atoms in each of the two hydrocarbon groups thereof, are found to be useful for the stabilization of polymers of a vinyl halide.

This application is a division of my application Ser. No. 510,424, filed Oct. .18, 1965, which is now US. Patent No. 3,321,499, and of my application Ser. No. 255,071, filed Jan. 30, 1963, which is now US. Patent No. 3,284,386. This invention relates to compounds useful for the stabilization of vinyl halide polymers, to methods or processes of making said compounds, to compositions including said compounds, and to vinyl halide polymers stabilized with said compounds and compositions. More particularly, it relates to asymmetric alkaline earth metal carboxylate-phosphites, to methods of male ing said phosphites, to compositions including said asymmetric compounds, and to v with said phosphites.

An important utilization of alkaline earth metal salts is in the field of vinyl halide resin additives, where alkaline earths are used rather generally as stabilizers or as components with other materials in stabilizing systems for vinyl resins in the form of carboxylates. These yl halide polymers stabilized alkaline earth carboxylates produce along with their important stabilizing effects of the metal a more or less degree of incompatibility due to the heretofore unavoidable excess of carboxylate that accompanies the metal, in the vinyl resin compound during its processing and in thefinished vinyl plastic product, as evidenced by the migration of unassimilated carboxylate to the surfaces of the vinyl resin compound during curing and processmg to cause undesirable plate-out on the carrying equipment and to cause undesirable scum that exudes :on ex posure and aging of the vinyl plastic to weathering and to cause undesirable surface interferences to decorative r utile printing and to heat-sealing of the vinyl plastic. The plate-out is noticed as a mist or as deposits on molds or calender [rolls producing molded objects or sheets having imperfect surfaces and requiring a considerable amount :of undesired cleaning of molds, casting surfaces, calender rolls and the like. This trouble is due to the presence of :two molecular equivalents of carboxylic acid for each mole of alkaline earth metal used as stabilizer. This amount is always an excess over what can apparently 'be contained compatibly with the needs for the amount of alkaline earth metal by the requirements to stabilize the vinyl resin during processing or in the finished plastic. Formulators and compounders in the vinyl industry have been obliged to contend with this problem whenever they required the presence of an alkaline earth stabilizer, and have made recourse to tedious and complicated correctives to overcome :it, not always with assurance of success. If the resin is fused and cured at 3'50-400 F. or higher, the plate-out is reduced. However, this requires exacting control which is very often impractical in factory operations, and such temperatures even for short .times result in some degradation of the vinyl polymer even under the best conditions. Accordingly, it .is a primary object of this invention .to avoid the difiiculties alluded to hereinabove and to provide a new alkaline earth metal salt stabilizer compound for vinyl halide polymers which does not exhibit plate-out over an extended period of time and which does not exhibit undesirable surface scum nor interferences to printing or heat sealing.

Another object of this invention is to provide novel methods for making these alkaline-earth metal salt compounds.

Yet another object is to provide compositions useful for stabilizing vinyl halide polymers andincluding a novel alkaline earth metal salt stabilizer compound.

A still further object is to :provide a new composition of a vinyl halide polymer containing said alkaline earth metal salt compound as a stabilizer and which .does not exhibit undesirable plate-out, surface scum or weathering, nor interference to printing or heat sealing.

These and other objects and advantages of the present invention will become more apparent .to those skilled in the art from the .following detailed description and examples.

According to the present invention, it has been discovered that vinyl halide polymers can be heat stabilized with a compound having the formula C) /OR R"CO-'M-OP where R and R" are selected from the group consisting of alkyl, cycloa'liphatic, aryl, aralkyl, and alkaryl radicals and their halogen substituted derivatives, where R has from 4 to 18 carbon atoms, where R has from 3 to 17 carbon atoms, and where M is selected from the group consisting of barium, calcium and strontium. Moreover, vinyl halide polymers stabilized with these asymmetric alkaline earth metal acid salt-organic phosphite compounds do not exhibit plate-out over extended periods of time, do not show surface scum nor feel slimy to the touch after aging, and do not exhibit undesirable surface interference to satisfactory surface printing or heat sealing as compared to vinyl halide polymers con- :taining the'alka'line earth metal carboxylic acid salt alone or with an organic phosphite. Thus, the problems alluded to hereinabove are avoided when these asymmetric alkaline earth metal salt-phosphites are employed in vinyl halide .polymers as stabilizers or are employed in conjunction -with other materials, such as conventional polyvinyl halide stabilizers of Iheclass of cadmium, zinc and/ or tin salts of organic acids with or without organic phosphites, to form stabilizing systems for vinyl halide polymers. Such asymmetric metal salt-phosphites contain only about half of the carboxylic content heretofore accompanying the alkaline earth metal. Although the reaction to produce these .asymmetric salts appears to be quantitative, it, of course, is possible that side reactions can occur or that the reactants may not have completely reacted, and small amounts of alkaline earth metal hydroxide, free phosphite, free acid, basic alkaline earth metal carboxylate, and alkaline earth metal dicarboxylate may be present. Thus, approximately overall amounts as from about 0:8 to 1.2 mole of carboxylic acid residue per mole of-alkaline earth metal may be present on analysis but are fully compatible for practical purposes during the processing of the vinyl resin and during aging of the vinyl plastic. The selected phosphites employed in the other half of the asymmetric alkaline earth salt to balance the requirement of the alkaline earth metal valency are known to be in themselves compatible in vinyl resins. Mixtures of these new asymmetric stabilizers can be used.

Examples of these asymmetric alkaline earth metal salt-phosphite compounds falling within the scope of this invention are barium butanoate-diphenyl phosphite, bari-um chlorovalerate-dibutyl phosphite, barium octoate-ditolyl phosphite, barium naphthenate-benzyl methyl phosphite, barium laurate-phenyl tolyl phosphite, barium benzoate-cyclopentyl phenyl phosphite, barium naphthoatediiodophenyl phosphite, barium naphthenate-octyl phenyl phosphite, calcium octoate-diphenyl phosphite, calcium octoate-octyl phenyl phosphite, calcium octoate-bis (nonyl phenyl) phosphite, calcium laurate-dicyclohexyl methyl phosphite, calcium chloro-palmitate-difluorobutyl phosphite, calcium S-methyl cyclopenthyl acetate-butyl phenyl phosphite, calcium phenyl acetate-ditolyl phosphite, calcium isocaproate-tridecyl phenyl phosphite, strontium octoate-octyl phenyl phosphite, strontium stearate-diphenyl phosphite, strontium octoate-bis (nonyl phenyl) phosphite, strontium camphonanate-bromohexyl tolyl phosphite, strontium p-toluate-diphenyl phosphite, strontium benzoate-octyl phenyl phosphite, strontium octoate-dicyclopentyl phosphite-strontium naphthenate-bis(dodecyl phenyl) phosphite, and the like.

These asymmetric alkaline earth metal phosphite salts can readily be prepared by dispersing in a particular diluent and/or solvent the alkaline earth metal hydroxide [Ba(OH) Ca(OH) or Sr(OH) or mixture thereof including their hydrates] and the desired phosphite, and then the required monocarboxylic acid is mixed in this dispersion at room temperature. When the exothermic reaction started reaches its peak, agitation is stopped, and after about one hour, the asymmetric alkaline earth salt herein described is formed. It appears the phosphite itself serves at first as the medium for the reaction of the metal hydroxide with the carboxylic acid, and only after that is formed and some time has elapsed does the phosphite enter the reaction. In addition it appears that the basic metal carboxylate formed thus in the presence of the phosphite is in a condition in which it is much more readily and completely reactive at lower temperatures than when it is formed separately.

The phenomena of this method of preparation can be observed readily as a rule, when (1) the solvent and/ or diluent, ether and/or hydrocarbon, is present with the phosphite into which the metal hydroxide is dispersed, and/or (2) excess of the phosphite itself is employed as the diluent. In these cases, when the acid is added to the hydroxide dispersion in the phosphite-diluent, within a very few minutes the exothermic reaction raises the temperature of the mixture to its peak and there is usually formed a gel or a hydrous suspension of the basic metal carboxylate in a mass generally too thick to stir. At this point no agitation is attempted, the mass is simply allowed to stand undisturbed, and about an hour later the whole mass becomes fluid and is converted to the asymmetric alkaline earth salt of this invention in a strikingly clear and neutral solution in the diluent/If desired, the gel can be stirred. The time of gellation, i.e., from the time the gel is for-med until it dissolves, will vary according to the batch size, reactants, diluents and/or solvents and so forth, so that it may vary from less than an hour to several hours.

In some instances it may not be necessary to apply external heat to the mixture. However, for practical usage,

to speed the reaction and to increase thefluidity of the mass, heat is generally applied to the mixture. Temperatures, thus, can be from about 50 F. to 400 F. Preferred temperatures are from about to 300 F. Al-.

though somewhat higher temperatures can be employed, temperatures should not be so high as to cause volatilization or degradation of the reactants, diluents and/or solvents, or products.

At the end of the above reaction the asymmetric alkaline earth metal salt-phosphite can be separated readily from the other materials present. However, this is not generally necessary since the small amount of water present, if not evolved during the reaction, is not deleterious in the vinyl halide polymer and in many instances will be removed during compounding and processing. Also, the water can be bound to or complexed with any free phosphite and sometimes With the asymmetric alkaline earth metal salt phosphite. The phenols produced are compatible with the vinyl halide polymers and may atford some antioxidant activity. Where diluents such as hydrocarbons and/or ethers are employed, these are also compatible with the vinyl halide polymers and can be retained.

In general, the organic phosphite, monocarboxylic acid and alkaline earth metal hydroxide are used in substantially, preferably in essentially equal, molar quantities. For example the reaction can proceed as follows:

M, R and R" have the same significance as indicated supra. R, however, is always selected from the group consisting of aryl and 'alkaryl radicals.

In preparing these asymmetric stabilizers special equipment is not ordinarily required. The reactants may simply be reacted in a vessel open to the atmosphere or if desired under reflux. Inert atmospheres and so forth are not usually required. Agitation is desirable during at least a portion of the reaction. Since some of the materials used in the preparation may be flammable, such as the diluents, precautions should be observed by using water baths or steam for heating. If the exothermic heat of reaction becomes too high, cooling means should be provided.

The asymmetric alkaline earth metal salt phosphite is mixed with the vinyl halide polymer only in a minor amount by weight, alone or with other known stabilizers, sufiicient to heat stabilize the vinyl halide polymer. In general, there can be used from about 0.1 to 10 parts by weight of the asymmetric alkaline earth metal salt-phosphite stabilizer of the present invention based on parts by total weight of the vinyl halide polymer.

Carboxylic acids for use in reacting with the alkaline earth hydroxides can be fatty acids, aromatic acids, naphthenic acids and so forth. The acid should be one whose intermediate basic salt formed during the reaction, i.e.

able with these vinyl halide monomer(s) in minor amounts are vinyl acetate, vinylidene fiuoride, vinylidene chloride, vinylidene bromide, allyl alcohol, 3-butene-1-ol, phenyl vinyl ether, allyl acetone, diallyl phthalate, diallyl malonate, diallyl malate, diallyl phthalate, divinyl ether, trichlorofiuoroethylene, diallyl ether, acrylonitrile, methacrylonitrile, chloroacrylonitrile and the like and mixtures thereof. It is understood that the term polymer includes copolymer, interpolymer, terpolymer and graft polymer, etc. Mixtures of these polymers, copolymers, and the like can be used. Preferred are polymers prepared from vinyl chloride, or a major amount by weight of vinyl chloride and a minor about by weight of vinylidene chloride or vinyl acetate, for example a polymer of from about 86 to 98% by weight of vinyl chloride and from about 14 to 2% by weight of vinyl acetate. The vinyl halide monomers have the formula where x is fluorine, chlorine or bromine.

These polymers can be obtained by bulk, emulsion, solution or suspension polymerization by procedures well known to the art. The polymers to be stabilized can be any one or more of the calender grade, plastisol grade, coating grade, blotter type resins and so forth.

These stabilized vinyl halide polymers, furthermore, can be plasticized with well known plasticizers such as dioctyl phthalate, tricresyl phosphate, the nonmigratory polyester plasticizers, the Paraplexes, di-2-ethyl butyl azelate, dipropylene glycol dibenzoate, chlorinated biphenyl, epoxy type plasticizers, triethylene glycol di-(Z- ethyl hexoate), chlorinated paraffin, n-butyl acetyl ricinoleate, butyl acetoxy stearate, and others well known to the art. Other stabilizers, antidegradants (antioxidants), ultra violet absorbers, fillers, rubbers, resins, pigments, dyes, fungicides and other compounding ingredients can be mixed and blended with these polymers as is customary in the art. Examples of the same are epoxidized soybean oil and other epoxidized oils and esters, the orthohydroxy benzophenones, the alkylated 2-hydroxy phenyl benzotriazoles, aryl amines, alkylated phenols, 2,6-ditertiary butyl para cresol, carbon black, titanium dioxide, magnesium oxide, antimony oxide, silica, calcium silicate, phthalocyanine blue or green, mica, wood cellulose, glass fibers, metal flakes, styrene-acrylonitrile copoylmers, butadiene-acrylonitrile copolymers, rubbery polyesterurethanes, rubbery polyetherurethanes, acrylonitrile-butadiene-1,3-styrene graft polymers or copolymers and so forth, and mixtures of the same. The inorganic pigments and fillers may or may not, previous to addition, to the polymer have been treated with a coating or surface treating agent such as a halo organo silane, alcohol or polyhydroxy compound, isocyanate or polyisocyanate, amine or poly amine, etc.

As noted above the asymmetric alkaline earth metal stabilizers of this invention can be used with other known polyvinyl halide stabilizers to obtain the benefits of such known stabilizers. These other heat and light stabilizers can be any of the cadmium (II), tin (II) and zinc salts of organic acids useful as polyvinyl halide stabilizers such as cadmium oleate, (i.e., cadmium dioleate), cadmium octoate, cadmium stearate, cadmium naphthenate, cadmium laurate, cadmium 2-ethyl hexoate, stannous oleate (i.e., stannous dioleate), stannous octoate, stannous naphthenate, stannous stearate, stannous p-tert. butyl benzoate, zinc octoate (i.e., zinc dioctoate), zinc oleate, zinc naphthenate, zinc stearate, and the like, and mixtures thereof, wherein preferably each acid group attached to the metallic radical has from 6 to 18 carbon atoms. Organic phosphite stabilizers (useful among other things to stabilize against oxidation) for polyvinyl halides may also be used such as those described above (other than the asymmetric stabilizer of this invention) as well as other organic phosphites. Complex organic phosphite salts of cadmium or zinc may also be employed (for example,

the reaction product of zinc oxide and dioctyl hydrogen phosphite). Each organic group of these additional organic phosphites preferably has from 4 to 18 carbon atoms. Mixtures of these additional stabilizers can be employed. These additional stabilizers together with the asymmetric stabilizer of this invention are employed in a minor amount by weight sufficient to stabilize the vinyl halide polymer. In general, the total amount of these stabilizers employed, when the asymmetric stabilizer is used with the metal salts and/or organic phosphites, is from about 0.1 to 10 parts by weight per parts by weight of the vinyl halide polymer. The asymmetric stabilizer, metal salt and/ or organic phosphite are used in weight ratios to each other sufficient to obtain the desired stabilizing action in the vinyl halide polymer. However, it is preferred that when the asymmetric stabilizer is used with one or more of the above metal salts, the ratio by parts by weight of the total amount of the asymmetric stabilizer to the total amount of the cadmium, tin, and/ or zinc salt should be from about 1:5 to 5:1. When the asymmetric stabilizer is used with one or more organic phosphite stabilizers, the preferred ratio by parts by weight of the total amount of the asymmetric stabilizer to the total amount of the organic phosphite is from about 5:1 to 1:1. When mixtures of the metal salts and the organic phosphites are used with the asymmetric stabilizers, it is preferred that these same parts by weight ratios should apply.

The resulting stabilized polymers in suitable amounts can be dissolved in organic solvents and used for solution coating of or casting on cans, fiber containers, cardboard boxes, and the like. The polymers can be made into films or sheets for packaging purposes (bread wrappers), shower curtains and the like; can be printed with decorative colors and used as wall coverings; can be used as a backing material in the manufacture of pressure sensitive adhesive tapes; can be calendered into woven or non-woven fabric of synthetic or natural fibers to make upholstery material or luggage; can be used in the manufacture of cable jackets or electric wire insulation; can be used to make refrigerator and window gaskets; can be used in making toys and athletic goods, etc. Also, the stabilized vinyl halide polymers of this invention, particularly the vinyl chloride-vinyl acetate copolymers, are particularly useful in making floor tiles, phonograph records and so forth. The stabilized polymers of the present invention are especially useful in making plastisols which can be very liquid casting compositions or non-dripping dipping compositions. By use of suitable inert diluents or extenders known to the art these stabilized resins usually in the form of plastisols can be made into organosols. Furthermore, these stabilized vinyl halide polymers can also be compounded to form impact resistant, rigid polyvinyl chloride articles using appropriate amounts of polyurethanes, or styrene-acrylonitrile copolymers and/ or butadiene-acrylonitrile c0- polymers, or acrylonitrile-butadiene-styrene copolymers, etc., in order to make tubing, pipes, trays and so forth.

These compounding ingredients are employed in amounts well known to those skilled in the art.

The stabilizers of the present invention as well as the other compounding ingredients can be mixed with the vinyl halide polymer on a rubber mill or in a banbury or extruder at temperatures of 275 to 350 F. or dispersed in the vinyl halide polymer including plasticizer, pigment, etc., and cast or fused and cured at 275 to 350 F. as known to the art. In general, the temperatures and times used for mixing, fusing and/ or curing are those necessary to obtain the desired blending or mixing of the ingredients and desired physical properties without causing appreciable degradation of the vinyl halide polymer as is well known to those skilled in the art. They may also be mixed with the vinyl halide polymer in solvent and the solvent evaporated therefrom. They can also be mixed with a suspension or latex of the vinyl where A is H for an alkyl (group and n varies fromt) to 5. They can contain from about '6 to 18 carbon atoms and can have up to an average of 2.6 rings. Examples of acids used in this invention are butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, 2,3-d-ibromobutanoic acid, .isobutyric acid, lauric acid, myristic acid, palmitic acid, trimethyl acetic acid, stearic acid, isova-leric acid, benzoic acid, o-chlorobenzoic acid, phenyl butyric acid, :isocaproic acid, u-naphthoic acid, S-anthroic acid, .p-toluic acid, ethyl 'benzoic acid, cyclobutane carboxylic acid, 'chloro-cyclohexane carboxylic acid, cyclopentane carboxylic acid, cyclopentyl acetic acid, 3-methyl cyclopentyl acetic acid, camphonanic acid, 4-1nethyl cyclohexane carboxylic acid, 2,2;6-trimethyl cyclohexane carboxylic acid, '2,3,4-tr imethyl cyclopentene-3-carboxylic acid, a-carnpholytic acid and :so forth. Mixtures of the {acids :can be used. The acids contain =overall from 4 to 18 carbon atoms (or 3 to 17 carbon atoms plus the C(DOH group), and it .is preferred that their :ha'logen -:derivativcs kbe monohalogen substituted and more preferably be monochloro substituted. Branchchain .alkyl acids are very desirable. These acids and methods for making or obtaining them are well known to the art.

Organic phosphites for use in the practice of the present invention have the following general formula:

OR POR In the formula R is selected from the group-consisting of alkyl, cycloaliphatic, aryl, aralkyl and alkaryl radicals and their .halogen substituted derivatives having from 4 to ;18 carbon atoms, and R is selected from the group consistingof aryl and alkaryl radicals and their halogen substituted derivatives having from 6 to 18 carbon atoms. Mixtures of these phosphites can be used. Examples of .phosphites falling Within this formula are dibutyl phenyl phosphite, diheptyl phenyl phosphite, butyl diphenyl phosphite, isobutyl diphenyl .phosphite, hexyl diphenyl ,phos phite, varnyl ditolyl phosphite, triphenyl phosphite, octyl diphenyl phosphite, tris (nonyl phenyl) phosphite, trixylyl ,phosphite, dibenzyl phenyl phosphite, dicyclo- ;pentyl phenyl phosphite, di(cyclohexy1 methyl.) phenyl .phosphite, di(cyclopenty1 propyl) tolyl phosphite, -monoclilorodecyl diphenyl phosphite, trichlorophenyl phosphite, tribromo octyldecyl ditolyl phosphite, tetra fiuoro octyl diphenyl :phosphite, di(monofluoro octyl) naphthyl .phosphite, dodecyl diphenyl phosphite, nonyl diphenyl phosphite, tetra decyl ditolyl phosphite and so forth. It is preferred that the halogen derivatives be monohalogen substituted, .and, more preferably, 'be monochloro substituted. The organic phosphites are well known to the art. They can readily be derived from mixtures of alcohols and phenols, substituted phenols and so forth by reaction I with phosphorous trichloride and-separating the resulting organic chloride from the organic vphosphite.

Diluents can be one'or more inert, relatively-high boiling ,point hydrocarbons and/or ethers and mixtures of the same which .are liquid at the reaction temperatures and which .perform the function of diluent as well as solvent. Examples of the others and hydrocarbons which may also act as plasticizers in the vinyl halide polymer, are tripropylene glycol methyl ether, ethylene ,glycol monoethyl ether, :ethylene glycol phenyl ether, ethylene .glycol monome'thyl ether, ethylene glycol monobutyl ether, diethylene glycol .monomethyl ether, 'diethylene gly- -col monoethyl ether, diethylene glycol monobutyl ether, propylene .glycol methyl ether, dipropylene glycol methyl ether, ethylene .glycol para (sec.) butyl phenyl ether,

ethylene glycol ,para (-tert.) butyl phenyl ether, dipropylene glycol phenyl ether, propylene glycol ortho chloro aphenyl ether, propylene glycol para (see) butyl phenyl ether, propylene glycol ortho (sec.) butyl phenyl ether, propylene glycol para (tert.) butyl .phenyl ether, propylene glycol 4biphenylyl ether, propylene glycol :p-cyclohexyl phenyl ether, propylene glycol p-chloro phenyl ether, propylene glycol .2,-4-'dichloro phenyl ether, benzyl tbutyl ether, :diethylene glycol diet-hyl ether, 2-butoxy toluene, lphenoxy .hepta-ne, octyl ether, toluene, cyclo- 'heptane, ii-methyl octane, ethyl benzene, the xylenes, cumene, undecane, tetralin, anisole, tert. amyl benzene, diethyl benzene, risohex-yl benzene, 3-methyl biphenyl, 1,3- dimethyl cyclohexane, 2,6-dirnethyl heptane, dodecane, octane, pentadecane and so forth and mixtures thereof. These diluents and/or solvents should have a boiling point of .at least 230 F, For best results a mixture of the hydrocarbon and ether diluent and/ or solvent should be used. Excess phosphite can be used to speed the reaction :and serves '-to some extent as a diluent but does not avoid the necessity for using an ether and/or-hydrocarbon diluent. When ethers are used alone as diluent, it is desirable to have a mixture of relatively high and low boiling point ethers. Likewise When hydrocarbons are being used alone, a mixture of relatively high and low boiling point hydrocarbons .should desirably be employed. These solvents and/ or diluents are employed in an amount sufficient to .give the desired fluidity and solvency to the reaction mass and .to facilitate handling. In general, the amount of .diluent may vary from about 20 to by weightof the reaction mixture. The use of these diluents, also, aids .in latermixing-the asymmetric stabilizers with the .resin, ,plastisols and so forth.

An alternative method for making the asymmetric alkaline earth metal salt-phosphites is to react the starting materials .in stages. This is somewhat less desirable since extra steps and extra heat are involved and sometimes the final product exhibits plate-out after extended use because of ,poor reaction efiiciency and because more ofa mixture is obtained rather than an asymmetric compound. 'Howcver, suchmethod may be more convenient to employ for some manufacturing purposes and end uses. For example, the alkaline earth metal hydroxide and the monocarboxylic acid are reacted-in the diluent as follows.

0 M(OH)z R- 'OH HO-M-O-("J-R" Ho-H where R" and H have the significance as defined supra. The water may or may not be separated from the resulting product. The mixed half salt of the metal (i.e., basic calcium octaoate, basic strontium octoate, basic barium naphthenate, basic calcium benzoate, basic strontium laurate, basic barium chlorobutyrate and so .forth corresponding to the foregoing metal hydroxides and monocarboxylic acids) is then reacted with the desired organic where .H R,.R' and R" have the significance as defined above. The basic alkaline earth metal salt can be-obtained by the .method asshown above or by any other method known to those skilled in the art. The mol ratios employed and the temperatures used are "essentially the same as shown supra.

Polymers to -be stabilized with the stabilizers of this invention can be any vinyl halide .polymer obtained -by .polymerizing a polymerizable vinyl halide monomer, including mixtures of these .monomers, such as vinyl fluoride, vinyl chloride, and vinyl bromide, and copolymers of a major (total) amount of one or more of these vinyl halide monomers and a minor .amount, preferably not over ofat least one'other copolymerizable mono- .meric material .having from one :to two polymerizable -H C--C .groups. Examples of monomers copolymerizhalide .polymer .and the water removed by filtration or after coagulation, but this is not too'desirable as it .may

be diflicult :to get the-desired amount of stabilizer in -.oron the polymer and some may be lost in the water.

These asymmetric stabilibers can also be added initially :oraduring polymerization Jofthe vinyl halide polymer although-care should be exercised since their addition dur- :ing ;polymerization may affect conversion rates, molecular weight, particlesize, and soforth.

The following examples, in which all parts are parts by weight, will'serve to illustrate the present invention with more'particularity to those skilled in the art.

Example 'I.'Preparati0n of calcium octoate-diphenyl ph'osphite 50 parts of calcium hydroxide were dispersed in a mixture "of 98 parts of tripropylene glycol methyl ether and '137 parts of triphenyl phosphite in a'flask at a temperature of from about 60 to 70 P. Then there were rapidly added "to the resultingmixture in the flask under go'o'd agitation 98 'parts'of 2-ethyl hexoic acid. The temperature of the mixture in the flask rose to 160 F. External heat was *applied to the 'flask to raise the temperature of the mixture 'to about 240 F. When the temperature of the mixture reached from about 190 to 200 F., the mixture thickened considerably. External heat was removed as soon as the mixture was 'too viscous for stirring, and the mixture was allowed to stand undisturbed While cooling for about one hour after which the mixture thinned out. The mixture was then stirred and phite (M.W.-approx. 41 6). The efliciency of the reaction was about 90%.

Example II.Preparation of calcium octoateoctyl phenyl phosphite The method of this example was similar to Example I above. 41.3 parts of calcium hydroxide were dispersed :in aflask containing a mixture of 95.2 parts of ethylene glycol monoethyl ether and 40 .parts of a principally aliphatic hydrocarbon solvent having a boiling point over 300 F. at a temperature of from '60 to 70 F. along with 98 parts of octyl diphenyl phosphite (added at about same time as the calcium hydroxide). 80.5 parts of 2- ethyl hexoic acid were next added rapidly with good agitation. The temperature of the resulting mixture rose to about 130 F. External heat was then applied to the flask to raise the temperature of the mixture to 240 F. Whenthe temperature of the mixture reached about 190- 200 'F., the mixture thickened. Heat was removed and the mixture allowed to stand for about an hour undisturbed. After the mixture thinned out or its viscosity dropped, the mixture was then stirred and heated to 240 F. and then filtered hot. The resulting solution of ether, hydrocarbon and excess phosphite contained about 6.6% calcium as calcium octoate-octyl phenyl phosphite,

.ExampleJIL-Preparation of calcium octoaIe-bis (nonyl phenyl) ph'osphite ipersedin a mixtureof 76.2;parts ofethylen'erglycolmonoethyl ether and 82 parts of the hydrocarbon solvent of Example II -above in-a flask atatemperature of from 60 'to .7 0 F. along with .194.0,:parts of'tris (nonyl phenyl) phosphite .(added at the same -time as the calcium hydroxide) 8.1 .parts ofoctoieaoid we're next :added 'rapidly with good agitation. Thetemperature of the resulting mixture then rose to about 160 "F. External heat was then applied 5 to the flask -to raise the temperature of the mixture' to about 240 :F. -When the temperature 'ofthe mixture reached '190-200 F rther-mixture thickenedaExterml heat was removed, randsthezflask and'iits contents were'alslowed :to stand undisturbed .'-for about "one :hour, after which the mixture thinned :out. The mixture was then :stirred .while being heated :to 240 1F. "and filtered. The ether and hydrocarbon filtrate for solution obtained contained about 4:6 calcium :as calciumaoctoate-bis nonyl phenyl) ;phosphite,

Example I V.Preparati0n ofb'arium naphthenateaoctyl phenyl .phasphite 'This method'wa's similar to the previous examples. parts of barium hydroxide monohydrate were dispersed in a flask containing amixture at90" F. of 36 parts 'of 'tripropylene glycol 'methyl ether, 40 ,parts of ethylene .glyco'l monoethyl ether "and parts of a high boiling point hydrocarbonsolvent (similar to"Example'II above), along with 98 parts of octyl diphenyl phosphite. Then '138 parts of naphthenic acid'havin'g an acid value equal to 229 were added rapidly undergood agitation. The temperature of'the resulting mixture'rose to 130 FQExtern'al heat Was'then applied'to the flask to 'raisethe temperature of the mixture to about 240 F. When the temperature of the mixture reached about -200 F., vthe mixture thickened'considerably. External heat was removed, and the mixture allowed to'stand undisturbed for about one hour, after which the mixture thinned out. The mixture was next stirred while being heated to 240 F. and filtered. The filtrate or solution of ethers and hydrocarbon contained about 13% barium as barium naphthenate-octyl phenyl phosphite.

Example V;Preparati0n of strontium octoate-octyl phenyl phosphite The method of this example was the same as that of Example II above, except that strontium hydroxide was used in place of calcium hydroxide. The resulting'filtrate or solution contained similar amounts of strontium as strontium octoate-octyl'phenyl phosphite,

About 100 parts of emulsionpolymerized pla'stisol grade polyvinyl chlorideresin (Geon 121) were *mixedWith '65 parts of dioctyl phthalate'and 2 parts of-the'resulting filtrate or solution of Example I above, containing 6.3% Ca as-calcium octoate-diphenyl phosphite. Aportion of the resulting plastisol was cast as a film 'on -ahighly polish'ed chrome plated steel plate'(2'sq. in) and cured-(and fused) at 350 F. for 10 minutes. The cured film was then stripped from the plate, and the :surface of the chrome platewas visibly examined for plate-out (a mis'ty appearance or deposit). There was no plate-out. This procedure was repeated on the same plate for a total of'twenty times. After these "twenty-runs, there still was no plate'out.

Example VII The method=of this-example was the same as that of Example VI above, except'th'at an 'equivale'nt*amount 'ot calcium octoate-was usedin place of an equivalent amount of the calcium octoate residue in the calcium octoate-diphenyl phosphite in the resulting filtrate or solution of Example 1'. above, and no organic phosphite was used. After separately casting and curing the plastisol for only three times, the chrome plate showed evidence of platevout (deposits). No further runs were then made.

Example VIII diphenyl phosphite of Example 1 above was added to the plastisol. After separately casting and curing the plastisol for only three times, the chrome plate showed evidence of plate-out (deposits on the surface). After these three runs, no further runs were made.

Example IX The method of this example was the same as that of Example VI above, except that in place of the calcium octoate-diphenyl phosphite filtrate or solution there was used in different tests (A) an equivalent of the calcium octoate-octyl phenyl phosphite filtrate or solution of Example II above, (B) an equivalent of the calcium octoatebis (nonyl phenyl) phosphite of Example 111 above, (C) an equivalent of the barium naphthenate-octyl phenyl phosphite filtrate or solution of Example IV above, and (D) an equivalent of the strontium octoate-octyl phenyl phosphite solution of Example V above. In each instance after 20 separate runs with each of the formulations (A) to (D), there was no plate-out on the chrome plated steel sample.

Tests, also, were conducted in which plastisols were prepared according to the methods of Examples VI and IX above, except that they contained additionally cadmium 2-ethyl hexoate and zinc stearate as additional conventional color stabilizers in suitable amounts. The resulting plastisols were cast, cured, stripped and samples cut from the strips and placed in a Fade-Ometer (Atlas Electric Devices Co.) and subjected to ultraviolet light for 40 hours. Control samples were prepared and tested in the same way in the Fade-Ometer. The control samples were compounded in the same fashion as the test samples except that in place of the asymmetrical alkaline earth metal salt-phosphites of the present invention, there were used equivalent amounts of the free corresponding alkaline earth metal carboxylic acid salt and the free phosphite from which the asymmetric compounds of the present invention were made. The results of the accelerated light exposure tests showed that the cured plastisol films of the present invention exhibited the same resistance to discoloration as did the control samples. However, unlike the control samples, the surfaces of the polyvinyl chloride films containing the asymmetric stabilizers of the present invention were not slippery or slimy. Moreover, polyvinyl chloride films stabilized with the asymmetric stabilizers of this invention could easily be printed and heat sealed while polyvinyl chloride films containing mixtures of alkaline earth metal dicarboxylates and phosphites, Where the carboxylates and phosphites were the same as those used in making the asymmetric stabilizers, were printed and heat sealed only with difliculty.

While the present invention has been described with particular reference to the prevention of heat degradation of vinyl halide polymers by incorporating therewith the novel asymmetric alkaline earth-carboxylic acid-phosphite compounds disclosed herein, it will be appreciated that minor amounts of such asymmetric compound (alone or with other antidegradants) can be used likewise to retard or prevent degradation of organic substances subject to degradation (by heat, light, ozone, etc.) like the polystyrene, polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-propylene copolymers containing unsaturation, poly (cis) butadiene-1,3 having various amounts of 1,2 and 1,4 configuration (Ziegler type as well as polybutadienes made by other methods), butadiene-styrcne copolymers (resinous and rubbery), acrylonitrile-butadiene-styrene type copolymers and grafts, synthetic natural rubber and/ or balata (cis/trans Ziegler or other type polymers), butyl rubber, polyesterurethanes, olyetherurethanes, polyether-ester urethanes, poly amid s, nylon, butadiene-acrylonitrile type rubbers (Hycar or Paracril), neoprene, polyesters (Paraplexes, Dacron, etc.), chlorinated rubber, silicone rubbers, p-olyether rubbers and plastics, acrylates and methacrylates and their copolymers, alkyd resins, phenol-formaldehyde type resins, melamine type resins, the cellulosics, the monomers used to prepare such polymers, greases, natural rubber, balata, pine oils, terpenes, lubricating oils, fuel oils, gasoline, vegetable oils, and so forth, either alone, mixed with each other or with the vinyl halide polymer or copolymer. These asymmetric compounds are useful as well as a treating agent for other natural and synthetic organic materials.

It, furthermore, is to be understood that in accordance with the provisions of the patent laws and statutes, the particular compounds, compositions, products and methods shown and described herein are presented for purposes of explanation and illustration and that various changes and modifications of said compounds, compositions, products and methods can be made without departing from this invention.

What is claimed is:

1. A composition useful for the stabilization of vinyl halide polymers comprising (1) at least one compound having the general formula where R and R" are selected from the group consisting of alkyl, cycloaliphatic, aryl, aralkyl, and alkaryl radicals and their halogen substituted derivatives,

where R has from 4 to 18 carbon atoms,

where R" has from 3 to 17 carbon atoms, and

where M is selected from the group consisting of barium,

calcium, and strontium, and

(2) at least one compound selected from the group consisting of (A) and (B),

where (A) is at least one compound selected from the group consisting of cadmium, stannous, and zinc salts of carboxylic acids, and

where (B) is at least one organic phosphite other than (1). 2. A composition useful for the stabilization of vinyl halide polymers comprising (1) at least one compound having the general formula 0 O-R R"iioM-o-P where R and R" are selected from the group consisting of alkyl, cycloaliphatic, aryl, aralkyl, and alkaryl radicals and their halogen substituted derivatives, where R has from 4 to 18 carbon atoms, where R" has from 3 to 17 carbon atoms, where M is selected from the group consisting of barium,

calcium, and strontium, and (2) at least one compound selected from the group consisting of cadmium, stannous, and zinc smts of carboxylic acids, where each carboxylic group attached to the metal of (2) has from 6 to 18 carbon atoms, and where the parts by weight ratio of (l) to (2) is about 1:5 to 5:1. 3. A composition useful for the stabilization of vinyl halide polymers comprising 2 13 14 (l) at least one compound having the general formula of alkyl, cycloaliphatic, aryl, arlalky-l and alkaryl radicals and their halogen substituted derivatives, H where R has from 4 to 18 carbon atoms, R CO M O P Where R" has from 3 to 17 carbon atoms, and

where M is selected from the group consisting of barium, where R and R" are selected from the group consisting of calcium, and Strontium,

alkyl, cycloaliphatic, aryl, ar-alkyl, and alkaryl radicals at P338t 0H6 P Selected from the group C011- d their halogen Substituted derivatives, sisting of cadmium, stannous, and zinc salts of car- Where R has from 4 to 18 carbon atoms, bOXYIiC aclds, where R" h fro 3 t 17 carbon atoms, d Where each carboxylic acid group attached to the metal where M is selected from the group consisting of barium, 0f as from 6 to 18 carbon atoms, and

calcium, and strontium, a d (3) at least one organic phosphite other than (1) and (2) at least one organic phosphite other than 1) and wherein each Organic group of Said Phosphite has from wherein each organic group of said phosphite has from 4 to 18 Carbon atoms, 4 to 18 carbon to nd where the parts by weight ratio of (1) to (2) is about Where the parts by weight ratio of (l) to (2) is about 115 to and 5:1 to 1:1, where the parts by weight ratio of (1) to (3) is about 4. A composition useful for the stabilization of vinyl 511 i0 1 halide polymers comprising References Cited 1) at least one compound having the general formula 20 UNITED STATES PATENTS 0 3,293,327 12/1966 Hechenbleikner et al. 260-936 H 3,300,442 1/1967 Darby et al 260-4535 RG0M0P o LEON D. ROSDOL, Primary Examiner.

where R and R" are selected from the group consisting I. GLUCK, Assistant Examiner. 

4. A COMPOSITION USEFUL FOR THE STABILIZATION OF VINYL HALIDE POLYMERS COMPRISING 